DE3148693A1 - METHOD FOR PRODUCING 4,4'-DIAMINO-1,1'-DIANTHRIMIDES - Google Patents

Description

O OR
OD ι

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen , Bayerwerk

Central area

Patents, trademarks and licenses PG / äBc

Process for the preparation of 4,4 '»diamino-1 A ° -dianthrimides

The invention relates to a process for the production of 4,4'-diamino-1 ,, 1 "» dianthrimides , which is characterized in that a mixture of an optionally substituted 1 ρ 4 = diaminoanthraquinone and an optionally substituted 1- aminoanthraquinone in 30-60% strength H ₃ SO _4, preferably 40 = 60 Siger H ₂ SO ^ j, with peroxomonosulphuric acid or peroxodisulphuric acid _p vorzugsx the "? else be used in the form of the alkali or ammonium salts = oxidized and is subsequently reduced to approach" The two starting components are preferably used in the process according to the invention in a molar ratio of optionally substituted 1-aminoanthraquinone to optionally substituted 1,4 = diaminoanthraquinone such as 0.9; 1 to 1.4: 1, particularly preferably such as 1½ to 11½: 1.

It is recommended _{v to use} a finely divided mixture of the anthraquinones ο ■

In general, the Ossidation at temperatures of about 0. to about 40 ⁰ C, preferably about 10 C. to about 2O ⁰ C.

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Particularly preferred oxidizing agent in the form of potassium peroxodisulfate.

4,4'-Diamino-1,1'-dianthrimides can be essentially manufacture by two methods:

1. Condensation of optionally substituted 1-chloroanthraquinone with an optionally substituted 1-aminoanthraquinone with Küpfer catalysis according to a Ullmann reaction (Ulimann's Encyclopedia the tech. Chemie, Vol ", 7, p. 585, 3rd edition, 1974), nitration of the resulting, in 4,4'-position unsubstituted dianthrimide in borosulfuric acid and reduction of the 4,4'-dinitro-1,1'-dianthrimide obtained.

2. Condensation of optionally substituted 4-benzoylamino-1-chloroanthraquinone with optionally substituted 1-amino = 4-benzoylamino-anthraquinone with copper catalysis and saponification of the benzoylamino groups according to the. Procedure of CH-PS 573 959.

The oxidation of a mixture of 1,4-diaminoan.thraquinone and 1-aminoanthraquinone to 4,4'-D.iäminodianthrimide is known from Houben / Weyl (vol. 7, part 3, p. 213, 4th edition). According to this reference, the dianthrimide is said to be formed when the components mentioned are _{treated in 85 to 96% H 3} SO ₄ with manganese dioxide. The reworking shows that, especially in the highly concentrated H ₂ SO _4, the reaction does not take place at all or takes place with extremely unsatisfactory results in terms of yield and quality of the end product.

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Surprisingly, it succeeds according to the invention Process, in a short time, in good yields 4,4'-diaminodianthrimide of great purity.

It is particularly surprising

a) that the hydrolysis-sensitive anthraquinone-1,4-diimine formed as an intermediate under the oxidation conditions reacts almost quantitatively with 1-aminoanthraquinone _{in the highly hydrous H 2} SO _{4 to form 4,4'-diaminodianthrimide;}

b) that under the reaction conditions that which has already formed Dianthrimide or its quinonimine, if at all, only to a very small extent to 1,4-diaminoanthraquinone and hydrolyzed 4-amino-1-hydroxyanthraquinone will;

c) that, if at all, only to a very small extent the competitive reaction of the self-condensation of 1-aminoanthraquinone to amino-tri- or -poly-anthrimides according to DE-AS 1 085 991 takes place.

. The method according to the invention is known method continue through its simplicity, the brevity of implementation, the absence of organic solvents and Superior to heavy metal compounds. In addition, this process makes 4,4'-diaminodianthrimides easy accessible, which are difficult to produce by the known processes.

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Preferably in the case of the invention ^ n. Procedure per Moles of optionally substituted 1,4-diaminoanthraquinone about 1.0 to about 2.5 moles of oxidizing agent, preferably ", 0 moles to 2.2 moles are used.

By adding heavy metal salts or oxides, such as

MnO ₂ , KMnO ₇ ,,

CrO ₀ , K ₀ Cr ₀ O. ,, Na ₀ Cr ₀ O _n, among others, the oxide

3 '2 2 7' 2 2 tion can be accelerated. The addition of heavy metal compounds is preferably carried out in catalytic amounts.

For the reduction, the known reducing agents effective in a sulfuric acid medium such as ShCl ₂ ZFeSO ₄ , SO ₂ di- and trihydroxybenzenes, alkali salts of oxo and thio acids of low-valent sulfur and oxygen acids, of phosphorus of low oxidation states and their salts can be used. Preferred reducing agents are FeSO ₄ , Na ₂ SO ₃ , NaHSO ₃ and H ₃ PO ₃ , H ₃ PO ₂ and their alkali salts. It is of course also possible to use mixtures of the reducing agents mentioned.

. Preferably in the process 1 "Ämiriö ^ ähthraquinones the formula -

0 NH-R

(I)

in the

R is hydrogen, alkyl, in particular

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Cycloalkyl, in particular C ₃ ~ C ₇ ~ cycloalkyl, aryl, in particular phenyl and naphthyl "aralkyl, in particular phenyl" Cj = Cg = alkyl, where the hydrocarbon radicals mentioned can be substituted and

· L., R ,, L, R ₄ , R ₅ hydrogen, halogen, especially Cl and Br, "NO ₂ , -SO ₃ H ₁ , = COOH, -OH, HSIH ₂ , = CN, arylamino, especially phenyl = and naphthylamino, alkylamino, in particular Cj-Cg-alkylamino, alkyl, in particular C ₁ -Cg -alkyl, cycloalkyl, in particular Co-C ^ cycloalkyl, aryl, in particular phenyl and naphthyl, aralkyl, in particular phenyl-C ₁ -Cg-alkyl _i - Alkoxy, in particular C ₁ -Cg -AlkOXy and aryloxy, in particular phenoxy, are used.

R preferably represents hydrogen «

R ₁ , R ₂ , R ₃ , R ₄ , Re preferably represent hydrogen, Cl, Br, -SO ₃ H, -COOH, -OH, -NH ₂ , -CN, -NO ₃ , C ₁ -C ₄ - AIlCyI especially methyl and ethyl, phenyl _Q C ^ -C ^ -alkylamino, phenylamino.

Exemplary, should be mentioned? 1 "Aminoanthraquinones 1-Amino-5-chloroanthraquinone, 1- = amino = 8-chloro an thr ach inone _f 1-amino-S ^ -diohlöranthraquinone, 1 = aminoant! Irachinone-2-sulfonic acid, 1-aminoanthraquinone = 8 = sulfonic acid , 1-amino-6-hydroxyanthraquinone, 1,5 = diaminoanthraquinone, 1,8-diamino-. Anthraquinone, 1,5 ~ diamino ~ 4- = chloranthraquinone, 1-amino-5-nitroanthraquinone, 1 = -amino-8 - nitroanthraquinone, 1 amino-2-methylanthraquinone, 1 = amino-> 5-phenylaminoanthraquinone, 1-amino-8-phenylaminoanthraquinone, 1-amino-5-

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methylaminoanthraquinone, 1-amino-8-methylaminoanthraquinone.

In particular, 1,4-D! Aminoanthraquinones were used in the process according to the invention the formula

P ^H 2 '

^R 8 ° ^NH 2
used. In formula II denote:

R, -, R-, R _Q , R _n , R _1n hydrogen, halogen, in particular ο / ο y ι υ

Cl- and Br, -NO ₀ , -SO ₇ H, -COOH, -OH, -NH ₉ , -CN, arylamino, especially phenyl- and naphthylamines, alkylamino, especially C.-Cg-alkylamino, alkyl, especially C-- Cg-alkyl, cycloalkyl, in particular C ₃ -C ₇ cycloalkyl, aryl, in particular phenyl and naphthyl, aralkyl, in particular phenyl-C _r ..- Cg-alkyl. Alkoxy, especially C - Cg-alkoxy and aryloxy, especially phenoxy. Rg, R ~, Rg, R _Q , Rq preferably represent hydrogen, Cl, Br, -SO ₃ H, -COOH, -OH, -NH ₂ , -NO ₂ , -CN, C | -C ₄ -alkyl, in particular methyl and ethyl, C - C ₄ -alkylamino, pheny! amino.

For example:

1,4-diaminoanthraquinone, 1,4-diaminoanthraquinone-5-sulfonic acid, 1 _/ 4-diaminoanthraquinone-6-sulfonic acid, 1,4-diaminoanthraquinone-7-sulfonic acid, 1,4-diaminoanthraquinone-8-sulfonic acid, 1 ^ -diamino -S-chloranthraquinone, 1,4-diamino-6-chloranthraquinone, 1, ^ - Diamino - ^ - chloranthra-

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quinone, 1 ^ -Diamino-e-chloroanthraquinone, 1,4-diamino-5-br oman thr ach inon, 1,4-DIaInInO-O -bromoanthraquinone, 1,4-diamino-7-bromoanthraquinone, 1,4-diamino-8-bromoanthraquinone, 1,4-diamino-5,8-dichloroanthraquinone, 1,4-diamino-5-nitroanthraquinone, 1,4-diamino-2-methylanthraquinone, 1,4-diamino-2-carboxyanthraquinone, 1,4-diamino-2-nitroanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1,4-diamino-2,3-dicyananthraquinone.

If one replaces given in the method according to the invention ^ - if substituted 1-amino-anthraquinone by optionally substituted 1,5- or 1,8-diaminoanthraquinone, so when using 1.8 to 2.0 mol of 1,4-diaminoanthraquinone also the double conversion to tetraaminotrianthrimide according to

NH

NH,

reach.

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When the invention. In the process, a suspension of finely ground, optionally substituted 1-aminoanthraquinone and optionally substituted 1,4-diaminoanthraquinone in 30-60% H ₂ SO _{4 can be} oxidized to BfSVoUf-. added, the 1-aminoanthraquinone and the 1,4-diaminoanthraquinone are pasted one after the other, very particularly preferably pasted together for economic reasons, since this procedure has no disadvantages with regard to the quality of the products.

The oxidizing agent can be in water or in a sulfuric acid water -Mixture and the sulfuric acid mixture of the aminoanthraquinones are added dropwise. However, it is advantageous to add the aminoanthraquinones to the paste the oxidizing agent is added continuously or in portions. The addition of the oxidizing agent can within 0.5-5 hours.

The reaction of 1,4-quinoneimine with 1-aminoanthraquinone usually takes place rapidly even at low temperatures. For economic reasons and for reasons of stirability - especially in concentrated reaction - in implementing a temperature of -20 ° 1NC * G / particular 15-20 ⁰ C is preferred. The reaction is complete Ca ₄ "1-2 hours after the addition of the oxidizing agent. The course of the reaction can be followed analytically, for example

² S, the amount of starting components can be quickly determined by known chromatographic methods.

The amount of sulfuric acid used depends on the solubility of the aminoanthraquinones in sulfuric acid and

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^ g =

-η -

determined by the stirrability of the paste or oxidation melt. In general, from about 10 to about 40 parts by weight of 40-60% H ₃ SO _{4 are used} per part by weight of 1,4-diaminoanthraquinone

The reduction of the resulting quinone imines of the diaminodianthrimides can be carried out with reducing agents in bulk or in the form of, for example, aqueous solutions will. You can use both the oxidation melt add to the reducing agent as well as the reducing agent metering in the melt, the latter method of operation having the advantage that oxidation and reduction can be carried out in the same vessel. Heating can be used to complete the reduction.

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• J jg

* "»

example 1

52> O g of 1,4-diaminoanthraquinone (92%) and 47.0 g of 1-aminoanthraquinone (98%) are dissolved in 512 g of 96% H ₃ SO ₄ , and this solution is stirred well within. dropped into 460 g of water for 30 min. After cooling to about 15 ^° C., 110.0 g of potassium peroxodisulfate are introduced over the course of about 3 hours, with thorough stirring, and the batch is allowed to slowly warm ^{to 20 ° C.} The mixture is stirred 2-3 h at about 20 ⁰ C, then the melt into a mixture of 600 ml of water and 150 ml of 40% NaHSO ₃ solution and, after addition of a defoamer in 30 min. At 80-90 ⁰ C . After 30 min. at 80-90 ⁰ C is filtered hot with suction, washed neutral with water and dried at 100 ⁰ C. 97.4 g of 4,4'-diamino-1,1'-dianthrimide (81%) are obtained, which corresponds to 86% of theory.

Example 2

10.6 g of 1,4-diaminoanthraquinone (92%) and 15.5 g of 1-aminoanthraquinone-2-sulfonic acid sodium salt (90%) are added to 220 g of 96% H ₃ SO ₄ dropped into 220 g of water for about 30 minutes. After cooling to about 15 ⁰ C one carries. with thorough stirring 0.5 g of manganese dioxide, then within 2.5 h 22.0 g of potassium peroxodisulfate. One is still stirring. 2 - 3 h at ⁰ 15-2o C, is added to the dark brown melt 15.0 g SnCl. ₂ 2H ₂ O in 30 ml of concentrated hydrochloric acid and stir for 1-2 hours. Then, 500 g of water was diluted and heated to 80-90 ⁰ C, suction filtered and washed with 10% H ₃ SO _4,

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then washed with 50-60 ⁰ C hot water until neutral. After drying at 100 ⁰ C to obtain 18.7 g already quite pure 4,4'-diamine-1,1'-dianthrimid-3-sulfonic acid, which corresponds to 84% of theory. The potassium peroxodisulfate used can also be replaced by an equivalent amount of ammonium peroxodisulfate without any disadvantage.

Example 3

A solution of 10 _r 6 g of 1,4-diamonoanthraquinone 98% and 17.4 g of i-amino-anthraquinone-8-sulfonic acid sodium salt (80.4%) in 220 g of 96% H ₃ SO ₄ is under . stirring and cooling, then stirred into 220 g of water · After cooling to 15 ⁰ C to wear within 2 - 3 hours, a 22.0 g of potassium peroxodisulfate and stirred for a further 3 - 4 h at ⁰ 15-2o C. is then added dropwise 20 ml of aqueous H ₃ PO ₃ solution (73%) is stirred for 30 minutes and heated after addition of 6.0 g of FeSO ₄ . 7H ₂ O 1 h 1-2 h at 80-90 ⁰ C. After cooling, it is suctioned off, washed neutral with water and dried at 100 ⁰ C. 19.6 g of 4,4'-diamino-1,1'-dianthrimide-5-sulfonic acid (approx. 90%) are isolated.

Example 4

A solution of 10.0 g of 1,4-diaminoanthraquinone (92%) and 11.3 g of 8-amino-1-chloroanthraquinone (89%) in 180 g. 96% iger. H ₂ SO ₄ is added dropwise to 180 g of water in 30 minutes. After cooling to 10-? 15 ° C materials were charged within h% 21.0 g potassium peroxodisulfate and stirred for 3 - 4 h at 15 ⁰ C after. Then 40 ml are added dropwise with thorough stirring

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aqueous NaHSO ₃ solution ,, leaves (40% ig) 0.5-1 h at 20-25 ⁰ C stirred and heated for 30 minutes with the dropwise addition. 30 ml of aqueous NaHSO ^ solution (40% strength) .80-90 ⁰ C. It is filtered hot with suction, washed neutral with hot water and dried at 100 ⁰ C. Yield: 19.6 g of crude product. After purification via the sulfate, 15.6 g of 5-chloro-4,4'-diamino-1,1'dianthrimide are obtained, which corresponds to 83% of theory based on 1,4-diamino-anthraquinone.

Example 5

A solution of 10.6 g. 1,4-Diaminoanthraquinone (92%) and 15.3 g of 5-amino-1,4-dichloroanthraquinone (82%) in 180 g & 6% sulfuric acid are added dropwise to 180 g of water with cooling. At 15-20 ⁰ C to wear in the melt

23.0 g of potassium and can be 2-3 hours stirred at 15-20 ⁰ C. The dark melt is poured into a mixture. 500 ml of water and 200 ml of 40% NaHSO, solution and, after stirring for 0.5-1 h recently Due to 80-90 ⁰ C. It is filtered hot with suction, washed neutral with hot water and dried at 100 ⁰ C. After purification via the sulfate, it is isolated from 23.8 g of crude product

16.1 g of pure 5,8-dichloro-4,4'-diamino-1,1'-diathrimide, this corresponds to 74% of theory.

Example 6

A solution of 10 g of 1,4 _Λ 6-diaminoanthraquinone (92% pure) and 11.9 g in 220 g of 96% 1,5-diamino-4-chloranthrachinpn (98%) strength H ₃ SO ₄ in 230 g of water pasted that

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Melt oxidized with 22.0 g of potassium peroxodisulfate and worked up accordingly Example 5. 21.9 g of crude product are obtained, after purification via the sulfate 15.4 g of 5-chloro-4,4 ^l , 8-triamino-1,1'-dianthrimide.

Example 7

A solution of 10.0 g of 1,4-diaminoanthraquinone (92%) and 10.3 g of 1-amino-2-methylanthraquinone (91.5%) in 180 g of 96% H ₂ SO ₄ is made with cooling dropped into 170 g of water. At 15 ° C., 21.0 g of potassium peroxodisulphate are introduced over the course of 2-3 hours, and the dark melt is subsequently stirred for 2-3 hours. The workup and purification via the sulfate as described in Example 5 gives 20.5 g of crude product and 12 _r 3 g of pure 3-methyl-4,4'-diaminodianthrimid corresponding to 67% of theory.

Example 8

A solution of 12.2 g of 1,4-diaminoanthraquinone (92%) and 13.8 g of 1-methylaminoanthraquinone (89%) in 220 g of 96% H ₂ SO ₄ is pasted in 210 g of water. At 15 ^° C., 21.0 g of potassium peroxodisulfate are introduced within 2-3 hours, and the dark melt is subsequently stirred for 2-3 hours. Then 16.0 g of SnCl ₃ .2H ₂ O in 30 ml of conc. Hydrochloric acid is added, heated briefly to 80-90 ° C. after 1 h, filtered off with suction and washed with 20% H ₂ SO ₄ . 22.8 g of 4-amino-4'-methylamino-1,1'-dianthrimide (approx. 85-90%) are obtained.

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Example, 9 :

A solution of 10> 6 g of 1,4-diaminoanthraquinone (92 Iig) and 14.0 g of 1-phenylaminoanthraquinone (91%) in 220 g of 96% H ₂ SO ₄ is pasted in 220 g of water. At 15 ⁰ C

22.0 g of potassium peroxodisulfate are entered within 2-3 h. After 2-3 h stirring, the melt is poured into a mixture of 300 ml of water and 100 ml of 40% NaHSO ₃ solution and heated for 1 hour at 80-90 ⁰ C. It is suctioned off, with 30% H ₂ SO ₄ washed, then with hot water again

tral washed and dried ^{at 100 0 C.} 15.6 g of practically pure 4-amino-4'-phenylamina-1,1-dianthrimide are obtained.

Example 10

A solution of 10 _Λ 6 g of 1,4-diaminoanthraquinone (92%) and 10.6 g of 1,8-diaminoanthraquinone (96%) in 200 g of 96% H ₃ SO ₄ is pasted in 210 g of water, and the melt is oxidized ^{at 15 °} C. with 22.0 g of potassium peroxodisulfate. Working up as in Example 5 gives 22 _f 0 g of crude product and, after purification via the sulfate, 16.2 g of largely pure 4,4 ', 5-triamino * ¹ ! , 1'-dianthrimide.

Example 11

A solution of 22 _r 0 g. 1,4-Diaminoanthraquinone (92%) and 10.2 g of 1,8-diaminoanthraquinone (96%) in 220 g of 96% H ₂ SO ₄ are poured into a mixture of 220 g of water and 100 g while cooling. 50% iger. H ₂ SO ₄ . dripped. At about 10 ^° C., 45.0 g of potassium peroxodisulfate are introduced in 5 hours, and the dark melt is at 10-15 ^° C. for 10 hours

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touched. 15-2o at ⁰ C is added dropwise 100 ml of 40% NaHSO ₃ solution to, stirred for 30 minutes at 15-20 ⁰ C ,. gives 10.0 g FeSO ₄ . 7 H ₂ O and heated after 2-3 h at 8O ⁰ C. It is suctioned off hot; washed with hot water until neutral and dried at 1QO ⁰ C. 30.8 g of product are isolated which, in addition to the main product, the 4 ', 4 ", 4,5-tetramino-1/1';8.1" -trianthrimide, also contains 20-30% triaminodianthrimide.

Example 12

A solution of 10.6 g of 1,4-diaminoanthraquinone (92%) and 10% of 1,5-diaminoanthraquinone (99%) in 200 g of 96% H ₃ SO ₄ is pasted in 200 g of water, and the melt is oxidized at 10-15 ° C with 24.0 g of potassium peroxodisulfate. Working up as in Example 5 gives 17.5 g of 4,4'.8-triamino-i, 1'-dianthrimide, which is still contaminated with a little aminopolyanthrimides.

Example 13

A solution of 12.2 g of 1 ^ -diamino-S-nitroanthraquinone (93%) and 9.6 g of 1-aminoanthraquinone (98%) in 200 g of 90% H ₃ SO ₄ is pasted in 200 g of water . After cooling to 1O ⁰ C 21.0 g .Kaliumperoxodisulfat be entered in .h 2-3, and the melt is stirred for about 2 hours at 10-15 ⁰ C. 15.0 g of hydroquinone are then added and the mixture is heated briefly after about 30 minutes. 50-60 ° and sucks off naph cooling. The filter cake is first made with 40%. H ₂ SO ₄ , then washed neutral with hot water and dried ^{at 100 ° C.} This gives 17.4 g of a mixture of the isomers 5-nitro-4,4'-diamino-1,1'-dianthrimide and 8-nitro-4,4'-diamino-1,1'-dianthrimide, Le A 21 299

«Β

· V

this corresponds to 86% of theory.
Example 14

A solution of 12.5 g of 1,4-diamino-2,3-dichloro-anthraquinone (98%) and 9.6 g of 1-aminoanthraquinone (98%) in 180 g of 96% sulfuric acid is in 180 g Stir in water. After cooling to 10-15 ⁰ C, 22.0 g of potassium are entered h in 2-3, and the melt is stirred for hours at 15 to 20 ⁰ C 1-2. Working up and purifying as in Example 5 gives 17.7 g of 2,3-dichloro-4,4'-diamino-1,1'-dianthrimide.

Example 15 .

A solution of 15.0 g of 1,4-diamino-2,3-dicyano-anthraquinone (87%) and 10.5 g of 1-aminoanthraquinone (98%) in 230 g of 96% H ₂ SO ₄ is stirred into 220 g of water while cooling. At 10 ^° C., 25.0 g of potassium peroxodisulfate are introduced over the course of 2 hours. After 4 h at 10-15 ° C 20.0 g of Fe SO _4. 7H ₂ O are added and the melt is stirred for 4 h at 20-25 ⁰ C. After filtration with suction, washed neutral with water and dried at 100 ⁰ C to obtain 24.2 g of crude product, and after purification on the sulfate 17.9 g • 2,3-dicyano-4,4 '-d.iamino-1,1' - dianthrimide, which corresponds to 78% "of theory.

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Claims (1)

-Vf- 3U8693 Claims Process for the preparation of 4,4'-diamino-1,1'-dianthrimides, characterized in that a mixture of an optionally substituted 1,4-diaminoanthraquinone and an optionally substituted 1-aminoanthraquinone in 30-60% H ₂ SO ,, preferably 40-60% H ₃ SO ₄ , oxidized with peroxomonosulphuric acid or peroxodisulfuric acid, which are preferably used in the form of the alkali or ammonium salts, and the batch is then reduced. 2. The method according to claim 1, characterized in that. the starting components in a molar ratio optionally substituted 1-aminoanthraquinone optionally substituted 1,4-diaminoanthraquinone as 0.9: 1 to 1.4: 1, preferably as 1: 1 to 1.1: 1. 3.. Process according to Claims 1-2 _1, characterized in that a finely divided mixture of the anthrachinones is used. 4.. The method according to claims 1-3 ,. characterized, that one oxidizes with potassium peroxodisulfate. 5.. Method according to claims 1-4, characterized in that that one oxidizes in the presence of heavy metal oxides or salts. Le A 21 299 • · «χ aj ^v _v ,""; 6. The method according to claims 1-5, characterized in that that one 1-aminoanthraquinones of the formula NH-R (I) in the R is hydrogen, alkyl, in particular Cj-Cg-alkyl, • Cycloalkyl _r in particular C - ^ - Cy-cycloalkyl, aryl, in particular phenyl and naphthyl, aralkyl, in particular phenyl-C ^ Cg-alkyl, it being possible for the hydrocarbon radicals mentioned to be substituted, and R ₁ , R 2 # R ₃ / R4 / Rc hydrogen, halogen, especially Cl and Br, -NO ₂ , -SO ₃ H, -COOH, -OH, -NH ₂ , -CN, arylamino, especially phenyl- and naphthylamino, alkylamino, especially _Cj-Cg alkylamino, alkyl, in particular C ..- Cg-alkyl, cycloalkyl, in particular C ^ C ^ Cyclöälkyl, aryl, in particular phenyl and naphthyl, aralkyl, in particular phenyl-C ^ -CG-alkyl. Alkoxy, in particular C ₁ -Cg -AlkOXy and aryloxy, in particular phenoxy, are used. Process according to claims 1-6, characterized in that that one 1,4-diaminoanthraquinones of the formula Le A 21 299 P NH, R- (II) in which R, -, R ^, R ₀ / R _Q / Rm hydrogen, halogen, ins- ο / ö y ι υ special Cl and Br, -NO ₀ , -SO, H, -COOH, -OH-, -NH ₀ , -CN, arylamino, especially phenyl- and naphthylamino, alkylamino, especially C - Cg-alkylamino, alkyl, in particular C -C -alkyl, cycloalkyl, in particular C _{3 -C 7} -cycloalkyl, aryl, in particular phenyl and naphthyl, aralkyl, in particular phenyl-C -C -alkyl, alkoxy, in particular C -C -alkoxy and aryloxy, in particular phenoxy denote, begins. 8. Process according to claims 1-7, characterized in that there is a 1-aminoanthraquinone of the formula ₃ r WasI, in which R is hydrogen and R-, R is hydrogen, Cl, Br, -SO ₃ H, -COOH, -OH, -NH ₂ , -CN, -NO ₂ , Cj - ^ - alkyl, especially methyl and ethyl, Phenyl, C.-C ₄ -alkylamino, phenylamino, and a 1,4-diaminoanthraquinone of the formula II, in which Rg, R ₇ , R _Q , R ₉ , R _{10 are} hydrogen, Cl, Br, -SO ₃ H, -COOH, -OH, -NH ₂ , -CN, -NO ₃ , Cj-C ^ alkyl, in particular methyl and ethyl, C ^ C ₄ -alkylamino, phenylamino, are used. 9. The method according to claims 1 to 5, characterized in, that a mixture of 1,4-diaminoanthraquinone and 1-aminoanthraquinone is used. 10 Process for the production of Tetraaminotrianthri- Le A 21 299 - 20 - miden, characterized in that msi is a mixture from 1 mol of optionally substituted 1/5 or 1,8-diaminoanthraquinone and 1.8-2 mol of 1,4-diaminoanthraquinone according to claim 1 oxidized and reduced. Le A 21 299